International Journal of Scientific and Research Publications, Volume 2, Issue 6, June 2012

ISSN 2250-3153

Biodiesel Production and Process Optimization

Rajarshi Kar, Oindrila Gupta, Mukundu Kumar Das
Chemical Engineering Department, Heritage Institute of Technology, Kolkata, India

Abstract- In any case, they make it certain that motor-power

can still be produced from the heat of the sun, which is always
available for agricultural purposes, even when all our natural
stores of solid and liquid fuels are exhausted..
Rudolf Diesel.
In this project we have intended to prepare biodiesel from waste
mustard oil. To make it economically feasible, a proper balance
have to be struck between the raw material cost & the selling
price of biodiesel as well as that of the byproduct glycerin. The
variables affecting the yield and characteristics of the biodiesel
produced from used frying oil were studied, the achieved results
were analyzed and a set of recommendations were proposed.

II. REACTION INVOLVED

Esterification Reaction: The basic process of converting waste
oil to biodiesel is called Esterification. Carboxylic act reacts
readily with alcohols in the presence of catalytic amount of
mineral acids to yield compounds called esters. The process is
called esterification.
The esterification reaction is both slow and reversible. The
equation for the reaction between an acid RCOOH and an
alcohol R'OH (where R and R' can be the same or different) is:

Objective of the work:

To study the production of biodiesel from waste mustard oil and
its process optimization
Transesterification
I. INTRODUCTION

iodiesel refers to a vegetable oil- or animal fat-based diesel

fuel consisting of long-chain alkyl (methyl, propyl or ethyl)
esters. Biodiesel is typically made by chemically reacting lipids
(e.g., vegetable oil, animal fat (tallow)) with an alcohol.
Biodiesel is meant to be used in standard diesel engines and
is thus distinct from the vegetable and waste oils used to fuel
converted diesel engines. Biodiesel can be used alone, or blended
with petro-diesel. Biodiesel can also be used as a low carbon
alternative to heating oil.
Biodiesel is liquid which varies in color between golden and
dark brown depending upon the production feedstock. It is
immiscible with water, has a high boiling point and low vapor
pressure. Typical ethyl ester biodiesel has a flash point of about
130C, biodiesel has a density of about 0.88 gm/cm^3, less than
that of water. A biodegradable transportation fuel that contributes
no net carbon di oxide or sulfur emission to the atmosphere and
is low in particulate emission. Ultra Low Sulfur Diesel
fuel(ULSD) fuel, which is advantageous because it has virtually
no sulfur content. Biodiesel has very good lubricating properties,
significantly better than standard diesel which can prolong
engine's life. As a result, Biodiesel can now compete with other
alternative fuels and clean-air options for urban transit fleets and
government vehicles across the country. It is safe, biodegradable
and reduces air pollutants such as particulates, carbon monoxide
and hydrocarbon. A variation in biodiesel energy density is more
dependent on feedstock used than the production process.

Triglycerides (1) are reacted with an alcohol such as ethanol/

methanol (2) to give ethyl/ methyl esters of fatty acids (3) and
glycerol (4):
Animal and plant fats and oils are typically made of
triglycerides which are esters containing three free fatty acids
and the trihydric alcohol, glycerol. In the transesterification
process, the alcohol is deprotonated with a base to make it a
stronger nucleophile. Commonly, ethanol or methanol is used.
As can be seen, the reaction has no other inputs than the
triglyceride and the alcohol.
Normally, this reaction will precede either exceedingly
slowly or not at all. Heat, as well as an acid or base are used to
help the reaction proceed more quickly. It is important to note
that the acid or base are not consumed by the transesterification
reaction, thus they are not reactants but catalysts.
Almost all biodiesel is produced from virgin vegetable oils
using the base-catalyzed technique as it is the most economical
process for treating virgin vegetable oils, requiring only low
temperatures and pressures and producing over 98% conversion
yield (provided the starting oil is low in moisture and free fatty
acids). However, biodiesel produced from other sources or by
other methods may require acid catalysis which is much slower.
Since it is the predominant method for commercial-scale
production, only the base-catalyzed transesterification process
will be described below.
An example of the transesterification reaction equation,
shown in skeletal formulas:
During the esterification process, the triglyceride is reacted
with alcohol in the presence of a catalyst, usually a strong alkali
(NaOH, KOH, or Alkoxides). The main reason for doing a

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International Journal of Scientific and Research Publications, Volume 2, Issue 6, June 2012
ISSN 2250-3153

titration to produce biodiesel, is to find out how much alkaline is

needed to completely neutralize any free fatty acids present, thus
ensuring a complete transesterification. Empirically 6.25 g / L
NaOH produces a very usable fuel. One uses about 6 g NaOH
when the WVO is light in color and about 7 g NaOH when it is
dark in color.

and contributes to emulsion formation during the water wash. For

these cases, an acid catalyst such as sulfuric acid can be used to
esterify the FFAs to methyl esters as shown in the following
reaction:

The alcohol reacts with the fatty acids to form the mono-alkyl
ester (or biodiesel) and crude glycerol. The reaction between the
biolipid (fat or oil) and the alcohol is a reversible reaction so the
alcohol must be added in excess to drive the reaction towards the
right and ensure

Fatty Acid Methanol Methyl ester Water

Ester Hydrolysis

Soap Forming Reaction

Acid Catalyzed Pretreatment
Special processes are required if the oil or fat contains
significant amounts of FFAs. Used cooking oils typically contain
2-7% FFAs and animal fats contain from 5-30% FFAs. Some
very low quality feedstocks, such as trap grease, can approach
100% FFAs. When an alkali catalyst is added to these feed
stocks, the free fatty acids react with the catalyst to form
Soap and water as shown in the reaction below:

Fatty Acid Potassium Hydroxide Potassium soap Water

Up to about 5% FFAs, the reaction can still be catalyzed
with an alkali catalyst but additional catalyst must be added to
compensate for that lost to soap. The soap created during the
reaction is either removed with the glycerol or is washed out
during the water wash. When the FFA level is above 5%, the
soap inhibits separation of the glycerol from the methyl esters

This process can be used as a pretreatment to convert the

FFAs to methyl esters and thereby reduce the FFA level. Then,
the low FFA pretreated oil can be transesterified with an alkali
catalyst to convert the triglycerides to methyl esters . As shown
in the reaction, water is formed and, if it accumulates, it can stop
the reaction well before completion. Removal of this alcohol also
removes the water formed by the esterification reaction and
allows for a second step of esterification or proceeding directly to
alkali-catalyzed transesterification. Note that the methanol-water
mixture will also contain some dissolved oil and FFAs that
should be recovered and reprocessed.. Soapstock, a mixture of
water, soaps, and oil, is dried, saponified, and then esterified with
methanol or some other simple alcohol using an inorganic acid as
a catalyst. The procedure relies on a large excess of alcohol and
the cost of recovering this alcohol determines the feasibility of
the process.
When oils with free fatty acids are used, free fatty acids will
be turned into soaps by the alkali catalyst. As a result, the yield
of biodiesel is lowered for those oils, and the soap needs to be
removed. The process used cleaning the biodiesel is known as
washing, in particular used for removing soaps. This process
involves either bubbling water up through the biodiesel (after
glycerin separation), or mixing water down on the top and letting
it flow down through the biodiesel. Water pulls the soaps out of
biodiesel as it passes through. The water eventually settles to
bottom, and can be separated readily from the biodiesel.
Process Details
Feedstock: Waste Mustard Oil
Chemicals Required: Sodium hydroxide as a catalyst
for transesterification reaction, Ethanol as a reagent,
distilled water.
Equipments used: A batch reactor with condenser, a
stirrer, clamp, a heater, Digital temperature indicator ( 0
250 oC ),Thermometer ( 0 250 oC ) x 2 nose, Beaker
( 1 L capacity ) x 2 nos, Cylinder ( 1 L capacity ) x 2
nos, Conical flask ( 100 cm3 ) x 2 nos, Flash distillation
apparatus with mantel heater for 1 L flask, Separating
funnel Iron stand with ring holder ( 2 nos. ),Rubber tube
( inch dia. ) x 1 roll ( 50m ),measuring cylinder.
Pipette, glass rod, PET bottles for biodiesel storage, a
batch distillation unit, PH strip, filter paper.

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International Journal of Scientific and Research Publications, Volume 2, Issue 6, June 2012
ISSN 2250-3153

Making a small batch biodiesel using Waste Mustard

Oil:
Filter and dewater waste mustard oil by using filter
paper since it may contain contaminants which oil
acidic(rancid).
Waste mustard Oil (3L) is heated to 50-60 C for 10
minutes and then cooled.
Firstly, 30grms of sodium hydroxide is mixed slowly
with alcohol in a three-necked round bottom flask,
stirring continuously.
Oil is poured slowly in the prepared Sodium ethoxide
mixture with continuous stirring and then heated at
50-60 C for about 90 minutes.
The alkalinity of the oil is measured by using pH strip
during reaction. The color of the Ph strip shows the
mixture is alkaline.
Now the whole system should be cooled and the
mixture allowed settling for at least 12 hours. But we
kept it for three days.
At the end of three days, the mixture separated to
impure Biodiesel (upper layer) and impure Glycerin
(lower layer) using a separating funnel.
The separated layer of Biodiesel is then fed to a batch
distillation unit for the recovery of ethanol and water.
The temperature is maintained around 105 C.
The residue (biodiesel + soap) collected is taken in a
beaker.
The impure Biodiesel is washed with water. Two layers
are formed, upper layer being Biodiesel and the lower
layer being water.
Now the Biodiesel is separated from the water by a
separating funnel.
This Biodiesel may contain a small percentage of water
and so it is then dried by passing through silica gel.
The impure Glycerin (colored) is treated with activated
carbon and then filtered through a Buchner funnel.
The amount of Biodiesel, Alcohol (recovered) and
Glycerin are measured and noted.

III. BIODIESEL FROM WASTE MUSTARD OIL:

PROCESS STEPS
Heating of Oil
In order to speed up the reaction, the waste mustard must be
heated. The ideal temperature range is 50 C to 60 C. Heating
with electric elements is usually the easiest way to bring the oil
up to temperature. Heat the oil first to remove any water content.
Waste oil will probably contain water, which can slow down the
reaction and cause saponification (soap formation). The less
water in the oil the better. So waste mustard oil is heated to 5060C for 10 minutes and then cooled.
Proportion of Mustard oil, Sodium Hydroxide (alkali catalyst)
and Ethanol taken are as follows:
Mustard Oil: Volume (3 L) * Density (910 g/L) = 2730 g
Sodium Hydroxide : 1% of Oil = 1% of 2730 g

= 27.3 g
~ 300 g
Ethanol: 3 moles of 100% C2H5OH per mole of oil
= (3 * 138) g
= 414 g
So, for 90% alcohol, amount taken = (414/.90) g
= 460 g
~ 500g
Mixing of ethanol and catalyst
The purpose of mixing ethanol and the catalyst (NaOH) is to
react the two substances to form ethoxide. Firstly, NaOH is
mixed slowly with alcohol in a three-necked round bottom flask,
stirring continuously. NaOH does not readily dissolve into
ethanol. It is best to turn on the mixer to begin agitating the
ethanol and slowly pour the NaOH in. When particles of NaOH
cannot be seen, the ethoxide is ready to be added to the oil. This
can usually be achieved in 20 30 minutes.
Heating and mixing
Oil is poured slowly in the prepared Sodium ethoxide
mixture with continuous stirring and then heated at 50-60 C for
about 90 minutes. A full speed propeller coupled to an electric
motor works fine as a mixer. Too much agitation causes
splashing and bubbles through vortexing and reduces mix
efficiency. There should be a vortex just appearing on the
surface. Adjust the speed, or the pitch or size of the stirrer to get
the right effect. The transesterification process separates the ethyl
esters from the glycerin. Now the whole system should be cooled
and the mixture allowed settling for at least 12 hours. But we
kept it for three days.
Settling and separation
The ethyl esters (biodiesel) will be floating on top while the
denser glycerin will have congealed on the bottom of the
container forming a hard gelatinous mass. Then carefully decant
the biodiesel. This can be done by draining the reactants out of
the bottom of the container through a transparent hose. The semiliquid glycerin has a dark brown color and the biodiesel is honeycolored. Keep a watch on what flows through the sight tube.
When the lighter-colored biodiesel appears divert it to a separate
container. If any biodiesel stays with the glycerin it is easy to
retrieve it later once the glycerin has solidified. If you left the
mixture in the tank until the glycerin gelled, reheat the tank just
enough to liquify the glycerin again.
The separated layer of Biodiesel is then fed to a batch
distillation unit for the recovery of ethanol and water. The
temperature is maintained around 105 C. The impure Biodiesel
is washed with water. Two layers are formed, upper layer being
Biodiesel and the lower layer being water.
Now the Biodiesel is separated from the water by a
separating funnel. This Biodiesel may contain a small percentage
of water and so it is then dried by passing through silica gel.
Draining of Glycerol
After the transesterification reaction, one must wait for the
glycerol to settle to the bottom of the container. This happens
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International Journal of Scientific and Research Publications, Volume 2, Issue 6, June 2012
ISSN 2250-3153

because Glycerol is heavier then biodiesel. The settling will

begin immediately, but the mixture should be left a minimum of
eight hours (preferably 12) to make sure all of the Glycerol has
settled out. The Glycerol volume should be approximately 20%
of the original oil volume. The impure Glycerin (colored) is
treated with activated carbon and then filtered through a Buchner
funnel. Volume of glycerin obtained near about 690ml.
Soap residue:
Suspended in the biodiesel will also be some soapy residues.
These are the result of Na+ ions from the NaOH reacting with
water created when the ethanol bonds with the ester chains along
with any other water that was suspended in the oil. If the reaction
produces more than the usual amount of soap, this happens when
NaOH comes into contact with water before it has a chance to
react with the oil. In this case the excess water should have been
boiledoff.
The part of the process where it is vital to keep all water out
of the reaction is when making the sodium ethoxide. Keep the
vessels NaOH comes in contact with as dry as possible. The
chances of a good clean splitting of ester from glycerin with little
soap by-product are much better on a warm dry summer day than
on a damp winter day.
Washing Biodiesel
The purpose is to wash out the remnants of the catalyst and
other impurities. There are three main methods:

Water wash only (a misting of water over the fuel,

draining water off the bottom)
Air bubble wash (slow bubbling of air through the
fuel)
Air/water bubble wash (with water in the bottom of
the tank, bubbling air through water and then the
fuel)

Which method works the best is dependent on the quality of

the fuel. Washing Biodiesel with water is the oldest and most
common method of cleaning biodiesel. Raw unwashed biodiesel
is about 3% ethanol. Ethanol is a solvent; it captures soap and
other impurities and holds them dissolved in the biodiesel. Water
soaks up that ethanol, releasing impurities to be washed away
with water. Water washing is the most flexible way to purify
biodiesel.
The process of washing biodiesel involves mixing it with
water. Water is heavier than biodiesel and absorbs the excess
alcohol, sodium hydroxide, and soap suspended in it. After
washing and settling, the water and impurities in the water can be
drained from the bottom of the container. Several water cycles
are generally needed. The first water drained off the bottom of
the biodiesel will be milky, and the final wash water drained off
will be clear. Excess sodium hydroxide in biodiesel will form
soap when mixed with water, and it takes a while for the soap to
settle out.
Depending on the method use, it takes roughly as much as
biodiesel for a wash cycle. Initial washing must involve gently
mixing the formation of soap that will take time to settle out.
However, you want the mixing to be through and for the water to
be dispersed throughout the biodiesel oil. Mustard oil based will

have better cold weather flow characteristics than from coconut

oil or animal fat.

IV. OBSERVATION AND RESULTS

Amount of waste mustard oil taken = 3liter
Mustard oil density = 910g/l=2730g
Amount of catalyst (NaOH) taken = 30g
Amount of ethanol = 500ml
pH of mixture = 7(indicates alkalinity)
Volume of impure biodiesel after reaction (V1) = 2800ml (94%)
Amount of ethanol loss due to vaporization = 20ml
After Flash distillation,
Amount of ethanol recovered (V2) = 30ml
Volume of unwashed biodiesel (V3) = 2800ml
Volume of pure biodiesel = 2750ml
Comparative Study:
Characteristics
Diesel

Biodiesel

Color

Golden

Density, kg/m3

0.84

Golden and dark

brown
0.88

Flash point, C

60 to 80

130

Fire point, C

78

138

Viscosity,mm^2/s@40C

1.3-4.1

1.5-4.0

Aniline Point, C

42

54

Pour point, C (summer)

18

10

Calorific Value, MJ/L

38.3

36

Boiling Point, C

180 to 340

315 to 350

Comparative study between diesel and biodiesel

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International Journal of Scientific and Research Publications, Volume 2, Issue 6, June 2012
ISSN 2250-3153

Figure: Process Flow Chart for Production of Biodiesel And

By- product from waste Mustard Oil

Biodiesel: Physical Characteristics

Properties

Values

Color
Specific Gravity
Aniline Point C
Diesel Index
Cetane Number(CN)
Flash Point C
Fire Point C
Kinematic Viscosity @40C
Gross calorific value

Golden &Dark Brown

0.88
54 C
43
40
130 C
138 C
1.5 to 4.0
10800

American Petroleum Institute (API) gravity

Diesel Index (DI) = (Aniline point F*degree API)/100

Cetane Number =Diesel Index-3
Gross Calorific Value=12400-2100* ^2
where is the density
Suggestion for future work
Biodiesel is not yet cost competitive with petroleum diesel.
In order to become more competitive, it is crucial to lower the
production costs associated with biodiesel. The cost of raw

material consists of as much as 70-95% of the total production

cost of biodiesel. The raw materials include oil, alcohol and a
catalyst. In order to reduce the production cost, it is most
beneficial to use waste cooking oil, as this is readily available
and at a low price. Waste mustard oil presents problems in the
form of excess water and free fatty acid composition of the oil
The best catalyzed transesterification of waste mustard oil
with ethanol is most economic decision. An alkali catalyzed
reaction allows for a low temperature and pressure with high
conversion. An alkali catalyzed reaction would require an
esterification pretreatment step in order to reduce the
concentration of free fatty acids and dewatering process in order
to create biodiesel suitable for vehicle consumption.
The problem of solidifying the biodiesel from waste
vegetable oil in cold weather conditions should be rectified in
future work by some kind of additives which are cheaply
available in the market
The Future of Biodiesel fuel
BIO-DIESEL is diesel made from animate source (using
plant oil and animal fats). Bio-diesel is basically comprised of
short-alkyl esters, made from animal fats and plant seeds.
With increase in the demand of petroleum products the
prices of petrol & diesel are increasing world wide. This trend is
expected in years to come as the resources are also depleting.
Hence alternative sources of energy for running our generators,
automobiles etc. are being considered world wide.
The possibility of obtaining oil from plant resources has
aroused a great interest and in several countries, vegetable oil
after esterification being used as 'Biodiesel'.
Biodiesel is a nontoxic, biodegradable replacement of the
petroleum diesel. The vegetable oils are treated with alcohol
ethanol or methanol and alkali. The products of the reaction are
Biodiesel and glycerol. Chemically biodiesel is monoalkyl esters
of long chain fatty acid and its properties are similar to petrodiesel. The biodiesel can be used as 20% blend with petro-diesel
in existing engines without any modification. Both the edible and
non edible vegetable oils can be used as the raw materials for the
biodiesel. Considering the cost and demand of the edible oils the
non edible oils may be preferred for the preparation of biodiesel
in India.
Biodiesel is a substance that preserves air quality. This
type of fuel is designed to enhance the richness of a diesel
automobile. Various organizations are setup to control air
pollution and find new sources of fuels for vehicles. Not only
does biodiesel help the environment, it also assists people is
using a lower cost means of transportation. It is a more harmless
method than the now used petroleum diesel. Biodiesel is created
from nature oils and fats that can be gathered from anyones
gardens.
The future of biodiesel is growing. More companies are
offering this solution to the consumers. At this stage, only diesel
powered automobiles can use the new fuel. This is expected to
change in the upcoming years. The mounting concern of offshore oil as well as the environmental issues has groups in an
uproar. Already there are several types of companies using
biodiesel as their main source for transportation.
Biodiesel fuel also has its own advantages and
disadvantages. The biggest advantage of biodiesel is that it can
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International Journal of Scientific and Research Publications, Volume 2, Issue 6, June 2012
ISSN 2250-3153

play a significant role in reducing the harmful carbon dioxide

emissions. However, there do exist some drawbacks of biodiesel
which may become a hindrance in the introduction of biodiesel
as an alternative to the harmful carbon emitting fossil fuels.
Biggest advantage of biodiesel fuel is that it is non toxic and
biodegradable, which makes it one of the most environment
friendly alternative of power generation.
After completion of our actual experiment in the biodiesel
production, we have obtained our desired compatibility with
petroleum diesel. The flash point, pour point, calorific value, fire
point, kinematic viscosity, density etc has been satisfactory
taking into consideration the possibility of errors here. So our
observation is compatible within the limits of experimental errors

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Biodiesel Production and Fuel Quantity J. Van Gerpen
http://en.wikipedia.org/wiki/Biodiesel
Fernando, S., Hal, C. and Jha S., NOx Reduction from Biodiesel Fuels,
Energy & Fuels 2006, 20, pp. 376-382
Hancock, N., Global Biodiesel Market, Oilseeds WA, Biodiesel
Workshop, August 2005
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[10] Nitschke, W.R., Wilson, C.M.; Rudolf Diesel: Pioneer of the Age of
Power; University of Oklahoma Press; 1965.
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AUTHORS
First Author Rajarshi Kar, Chemical Engineering Department,
Heritage Institute of Technology, Kolkata, India, Email:

rajarshi.kar6@gmail.com
Second Author Oindrila Gupta, Chemical Engineering
Department, Heritage Institute of Technology, Kolkata, India, Email:

oindrilaa.gupta@gmail.com
Third Author Mukundu Kumar Das, Chemical Engineering
Department, Heritage Institute of Technology, Kolkata, India

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